US11819834B2ActiveUtilityA1

Aluminophosphate molecular sieve SCM-18, its preparation and application thereof

46
Assignee: CHINA PETROLEUM & CHEM CORPPriority: Oct 25, 2018Filed: Sep 19, 2019Granted: Nov 21, 2023
Est. expiryOct 25, 2038(~12.3 yrs left)· nominal 20-yr term from priority
B01J 29/83B01J 20/0292B01J 37/04B01J 37/06B01J 37/082C01B 39/54C01P 2002/72C01P 2006/12C01P 2006/14C01B 37/04B01J 20/18B01J 20/28011B01J 20/28061B01J 20/28071B01J 20/3078B01J 20/3085B01J 20/02
46
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Cited by
22
References
20
Claims

Abstract

An aluminophosphate molecular sieve SCM-18 has a schematic chemical composition, expressed on a molar basis, of Al2O3.n P2O5, in which n represents a phosphorus to aluminum molar ratio, and is in a range of about 0.8-1.2. The aluminophosphate molecular sieve has a unique X-ray diffraction pattern, and can be used as an adsorbent, a catalyst or a catalyst carrier.

Claims

exact text as granted — not AI-modified
The invention claimed is: 
     
       1. An aluminophosphate molecular sieve having a schematic chemical composition of Al 2 O 3 ·nP 2 O 5 , expressed in molar ratio, wherein n represents a phosphorus to aluminum molar ratio, and is in a range of about 0.8 to about 1.2, and the molecular sieve has an X-ray diffraction pattern exhibiting a relative intensity profile as shown in the following table: 
       
         
           
                 
                 
                 
                 
               
                     
                     
                 
                     
                   2 theta 
                   Interplanar spacing 
                   Relative intensity 
                 
                     
                   (°) 
                   (Å) 
                   (I/I 0 ) × 100 
                 
                     
                     
                 
                     
                   8.20-8.60 
                   10.27-10.77 
                   VS 
                 
                     
                   13.73-13.99 
                   6.32-6.44 
                   VS 
                 
                     
                   16.16-16.41 
                   5.39-5.48 
                   W-M 
                 
                     
                   16.36-16.61 
                   5.33-5.41 
                   W-M 
                 
                     
                   21.34-21.58 
                   4.11-4.16 
                   W-M 
                 
                     
                   21.66-21.91 
                   4.05-4.10 
                   M-S 
                 
                     
                   24.04-24.32 
                   3.66-3.70 
                   W-M. 
                 
                     
                     
                 
             
                
                
                
                
               
               
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
       2. The aluminophosphate molecular sieve of  claim 1 , wherein the molecular sieve has an X-ray diffraction pattern exhibiting a relative intensity profile shown in the following table: 
       
         
           
                 
                 
                 
                 
               
                     
                     
                 
                     
                   2 theta 
                   Interplanar spacing 
                   Relative intensity 
                 
                     
                   (°) 
                   (Å) 
                   (I/I 0 ) × 100 
                 
                     
                     
                 
                     
                   8.20-8.60 
                   10.27-10.77 
                   VS 
                 
                     
                   13.73-13.99 
                   6.32-6.44 
                   VS 
                 
                     
                   13.90-14.20 
                   6.23-6.36 
                   W-M 
                 
                     
                   16.16-16.41 
                   5.39-5.48 
                   W-M 
                 
                     
                   16.36-16.61 
                   5.33-5.41 
                   W-M 
                 
                     
                   19.66-19.91 
                   4.45-4.51 
                   W 
                 
                     
                   21.34-21.58 
                   4.11-4.16 
                   W-M 
                 
                     
                   21.66-21.91 
                   4.05-4.10 
                   M-S 
                 
                     
                   24.04-24.32 
                   3.66-3.70 
                   W-M 
                 
                     
                   24.41-24.65 
                   3.61-3.64 
                   W-M 
                 
                     
                   25.71-25.96 
                   3.43-3.46 
                   W-M. 
                 
                     
                     
                 
             
                
                
                
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
       3. The aluminophosphate molecular sieve according to  claim 2 , wherein the molecular sieve has an X-ray diffraction pattern exhibiting a relative intensity profile shown in the following table: 
       
         
           
                 
                 
                 
                 
               
                     
                     
                 
                     
                     
                   Interplanar spacing 
                   Relative intensity 
                 
                     
                   2 theta (°) 
                   (Å) 
                   (I/I 0 ) × 100 
                 
                     
                     
                 
                     
                   8.20-8.60 
                   10.27-10.77 
                   VS 
                 
                     
                   13.73-13.99 
                   6.32-6.44 
                   VS 
                 
                     
                   13.90-14.20 
                   6.23-6.36 
                   W-M 
                 
                     
                   16.16-16.41 
                   5.39-5.48 
                   W-M 
                 
                     
                   16.36-16.61 
                   5.33-5.41 
                   W-M 
                 
                     
                   17.17-17.42 
                   5.08-5.16 
                   W 
                 
                     
                   19.66-19.91 
                   4.45-4.51 
                   W 
                 
                     
                   21.34-21.58 
                   4.11-4.16 
                   W-M 
                 
                     
                   21.66-21.91 
                   4.05-4.10 
                   M-S 
                 
                     
                   24.04-24.32 
                   3.66-3.70 
                   W-M 
                 
                     
                   24.41-24.65 
                   3.61-3.64 
                   W-M 
                 
                     
                   25.71-25.96 
                   3.43-3.46 
                   W-M 
                 
                     
                   27.85-28.12 
                   3.17-3.20 
                   W-M 
                 
                     
                   28.18-28.43 
                   3.13-3.16 
                   W 
                 
                     
                   29.40-29.66 
                   3.01-3.03 
                   M. 
                 
                     
                     
                 
             
                
                
                
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
       4. The aluminophosphate molecular sieve according to  claim 1 , wherein the molecular sieve has a specific surface area of about 150-500 m 2 /g, and a micropore volume of about 0.9-0.25 ml/g. 
     
     
       5. A method for preparing an aluminophosphate molecular sieve according to  claim 1 , comprising the steps of:
 i) providing an aluminophosphate molecular sieve precursor, wherein the precursor has an X-ray diffraction pattern exhibiting a relative intensity profile as shown in the following table: 
 
       
         
           
                 
                 
                 
                 
               
                     
                     
                 
                     
                   2 theta 
                   Interplanar spacing 
                   Relative intensity 
                 
                     
                   (°) 
                   (Å) 
                   (I/I 0 ) × 100 
                 
                     
                     
                 
                     
                   8.20-8.38 
                   10.54-10.77 
                   S-VS 
                 
                     
                   13.40-13.61 
                   6.50-6.60 
                   M-S 
                 
                     
                   15.81-15.99 
                   5.54-5.60 
                   S-VS 
                 
                     
                   16.75-16.97 
                   5.22-5.28 
                   W-M 
                 
                     
                   20.82-21.09 
                   4.21-4.26 
                   S-VS 
                 
                     
                   22.31-22.52 
                   3.94-3.98 
                   S-VS 
                 
                     
                   23.49-23.68 
                   3.75-3.78 
                   M, 
                 
                     
                     
                 
             
                
                
                
                
               
               
                
                
                
                
                
                
                
                
               
            
           
         
       
       and
 ii) calcining the aluminophosphate molecular sieve precursor to obtain the aluminophosphate molecular sieve. 
 
     
     
       6. The method according to  claim 5 , wherein the precursor has an X-ray diffraction pattern exhibiting a relative intensity profile as shown in the following table: 
       
         
           
                 
                 
                 
                 
               
                     
                     
                 
                     
                   2 theta 
                   Interplanar spacing 
                   Relative intensity 
                 
                     
                   (°) 
                   (Å) 
                   (I/I 0 ) × 100 
                 
                     
                     
                 
                     
                   8.20-8.38 
                   10.54-10.77 
                   S-VS 
                 
                     
                   13.40-13.61 
                   6.50-6.60 
                   M-S 
                 
                     
                   15.81-15.99 
                   5.54-5.60 
                   S-VS 
                 
                     
                   16.75-16.97 
                   5.22-5.28 
                   W-M 
                 
                     
                   19.59-19.86 
                   4.46-4.53 
                   W 
                 
                     
                   20.82-21.09 
                   4.21-4.26 
                   S-VS 
                 
                     
                   22.31-22.52 
                   3.94-3.98 
                   S-VS 
                 
                     
                   23.49-23.68 
                   3.75-3.78 
                   M 
                 
                     
                   23.88-24.16 
                   3.65-3.72 
                   W-M 
                 
                     
                   25.15-25.42 
                   3.50-3.54 
                   W-M 
                 
                     
                   25.54-25.82 
                   3.45-3.48 
                   W-M 
                 
                     
                   27.16-27.44 
                   3.25-3.28 
                   W-M 
                 
                     
                   29.54-29.82 
                   2.99-3.02 
                   W-M. 
                 
                     
                     
                 
             
                
                
                
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
       7. The method according to  claim 5 , wherein the step i) further comprises:
 ia) mixing an aluminum source, a phosphorus source, an organic material R and water at a molar ratio of the aluminum source (calculated as Al 2 O 3 ): the phosphorus source (calculated as P 2 O 5 ):R:H 2 O of about 1:(1.0-3.0):(1.5-6.0):(50-500) to obtain a synthetic mother liquor; and 
 ib) subjecting the synthetic mother liquor to crystallization to obtain the aluminophosphate molecular sieve precursor, 
 wherein the organic material R is an ammonium hydroxide having the following formula: 
 
       
         
           
           
               
               
           
         
         wherein the groups R1-R12, which may be identical or different from each other, are independently selected from H and C 1-6  alkyl groups, and 
         the groups R13 and R14, which may be identical or different from each other, are independently selected from C 1-6  alkyl groups. 
       
     
     
       8. The method according to  claim 7 , wherein in step ia) the aluminum source, the phosphorus source, the organic material R and water are mixed at a molar ratio of the aluminum source (calculated as Al 2 O 3 ): the phosphorus source (calculated as P 2 O 5 ):R:H 2 O of about 1: (1.0-2.0):(2.5-4.8):(100-300). 
     
     
       9. The method according to  claim 7 , wherein the organic material R is 1,1-[1,4-phenylenebis(methylene)]bis-1-methylpyrrolidinium dihydroxide. 
     
     
       10. The method according to  claim 7 , wherein step ib) is carried out under the following conditions:
 a sealed reaction vessel, a crystallization temperature of about 130-200° C., and a crystallization time of about 24-150. 
 
     
     
       11. The method according to  claim 7 , wherein the aluminum source is one or more selected from the group consisting of pseudo-boehmite, aluminum isopropoxide, aluminum sol, aluminum hydroxide, aluminum sulfate, aluminum chloride and aluminum oxide;
 and/or the phosphorus source is one or more selected from the group consisting of phosphoric acid, orthophosphorous acid and phosphorus pentoxide. 
 
     
     
       12. The method according to  claim 5 , wherein the aluminophosphate molecular sieve precursor has a molar ratio of phosphorus, calculated as P 2 O 5 , to aluminum, calculated as Al 2 O 3 , in a range of about 0.8 to about 1.2, and
 optionally, the aluminophosphate molecular sieve precursor comprises from about 8 wt % to about 40 wt % of an organic material, based on the weight of the aluminophosphate molecular sieve precursor. 
 
     
     
       13. A molecular sieve composition comprising an aluminophosphate molecular sieve according to  claim 1 , and a binder. 
     
     
       14. A method for treating automobile exhaust gas, comprising contacting a catalyst comprising the aluminophosphate molecular sieve to  claim 1  loaded with copper with the automobile exhaust gas to cause decomposition of nitrogen oxides in the automobile exhaust gas. 
     
     
       15. A method for removing water from a water-containing material to be dried, comprising: contacting the molecular sieve composition according to  claim 13  with the water-containing material, whereby the molecular sieve composition adsorbs water from the water-containing material, wherein the water-containing material is an organic solvent or natural gas. 
     
     
       16. The aluminophosphate molecular sieve according to  claim 4 , wherein the molecular sieve has a specific surface area of about 200-400 m 2 /g; and a micropore volume of about 0.10-0.20 ml/g. 
     
     
       17. The method according to  claim 6 , wherein the precursor has an X-ray diffraction pattern exhibiting a relative intensity profile as shown in the following table: 
       
         
           
                 
                 
                 
                 
               
                     
                     
                 
                     
                   2 theta 
                   Interplanar spacing 
                   Relative intensity 
                 
                     
                   (°) 
                   (Å) 
                   (I/I 0 ) × 100 
                 
                     
                     
                 
                     
                   8.20-8.38 
                   10.54-10.77 
                   S-VS 
                 
                     
                   8.80-9.06 
                    9.75-10.04 
                   W 
                 
                     
                   13.40-13.61 
                   6.50-6.60 
                   M-S 
                 
                     
                   14.13-14.39 
                   6.15-6.26 
                   W 
                 
                     
                   15.81-15.99 
                   5.54-5.60 
                   S-VS 
                 
                     
                   16.75-16.97 
                   5.22-5.28 
                   W-M 
                 
                     
                   19.59-19.86 
                   4.46-4.53 
                   W 
                 
                     
                   20.82-21.09 
                   4.21-4.26 
                   S-VS 
                 
                     
                   21.54-21.84 
                   4.06-4.12 
                   W 
                 
                     
                   22.31-22.52 
                   3.94-3.98 
                   S-VS 
                 
                     
                   23.49-23.68 
                   3.75-3.78 
                   M 
                 
                     
                   23.88-24.16 
                   3.65-3.72 
                   W-M 
                 
                     
                   25.15-25.42 
                   3.50-3.54 
                   W-M 
                 
                     
                   25.54-25.82 
                   3.45-3.48 
                   W-M 
                 
                     
                   26.20-26.41 
                   3.37-3.40 
                   W 
                 
                     
                   27.16-27.44 
                   3.25-3.28 
                   W-M 
                 
                     
                   28.66-28.90 
                   3.08-3.11 
                   W 
                 
                     
                   29.54-29.82 
                   2.99-3.02 
                   W-M. 
                 
                     
                     
                 
             
                
                
                
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
       18. The method according to  claim 7 , wherein wherein in the formula of the organic material R, the groups R1-R12, which may be identical or different from each other, are independently selected from from H and C 1-3  alkyl groups; and
 the groups R13 and R14, which may be identical or different from each other, are independently selected from C 1-3  alkyl groups. 
 
     
     
       19. The method according to  claim 10 , wherein step ib) is carried out under the following conditions: a sealed reaction vessel, a crystallization temperature of about 145-185° C., and a crystallization time of about 48-120 hours. 
     
     
       20. The method according to  claim 11 , wherein the aluminum source is selected from the group consisting of pseudo-boehmite and aluminum isopropoxide; and the phosphorus source is phosphoric acid.

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